Title of Invention

A PROCESS FOR THE PREPARATION OF COPPER BOUND BIS (PICOLYL) AMINE POLYMER

Abstract A process for the preparation of copper bound bis (picolyl) amine polymer by reacting macroporous bis (picolyl) amine polymers in the presence of copper salts in an aqueous medium at a pH of 2 to 6 or organic solvent at a temperature in the range of 25 to 35°C, for a period ranging from 12 to 24 hours, removing the macroporous copper ion containing bis (picolyl) amine polymer by conventional methods, followed by washing and drying by known method to obtain copper bound bis (picolyl) amine polymer.
Full Text This invention relates to a process for the preparation of copper bound bis (picolyl) amine polymer. More particularly it relates to a process for the preparation of copper bound to macroporous bis (picolyl) amine polymers. The macroporous bis (picolyl) amine polymers used in the process of this invention, have general formula 1 and R = (2-picolyl), (3-picolyl) having formula 2 and 3 respectively in the drawing accompanying this specification. The copper chelated macroporous bis (picolyl) amine polymers thus obtained are useful catalysts in oxidative coupling reactions of 2,6-disubstituted phenols to yield a class of polymers known as poly (phenylene oxide).
Poly (phenylene oxiee) is an important class of engineering polymer. The polymer as prepared is difficult to process and is normally modified with blending with high impact polystyrene to overcome the processing difficulties. The modified polymer finds applications in many varied areas ranging from automotive, electrical and consumer industries.
In our copending application number 790/D/97, we have described and claimed a process for the preparation of macroporous bis (picolyl) amine polymers. The bis (picolyl) amine prepared by the said process can be further reacted under suitable reaction conditions to incorporate copper ions to get copper chelated bis (picolyl) amine polymers.
The conventional processes of polymerization to get poly (phenylene oxide) are based on the following reactions :

(a) Oxidative coupling reaction of 2,6-disubstituted phenols,
(b) Free-radical initiated displacement reaction using some
oxidizing agent as initiator and
(c) Displacement reaction using high temperatures.
The most favoured process for the preparation of poly (phenylene oxide) is by oxidative coupling reaction of 2,6-disubstituted reactions. A typical polymerization involves 2,6-dimethyl phenol being polymerized at temperatures in the range of 25 to 50°C, in the presence of a catalyst and vigorous stirring under a stream of oxygen. The catalyst is a copper halide and pyridine or aliphatic amine. The reactions are exothermic in nature and proper cooling has to be maintained to get the product of desired acceptability. In these systems the ratio of copper to nitrogen
is very crucial and necessitates the use of large quantities of pyridine or the other nitrogen contributing component to be added
in the reaction. An important engineering plastic poly(phenylene
oxide) (PPO) is commercially produced by the oxidative coupling
reaction of 2,6-dimethyl phenol.
The process however suffers from the following disadvantages :
(a) The presently used system comprises of copper halide,
pyridine and oxygen. This is a homogenous system with high
concentration of pyridine.
(b) Since the catalyst system is homogeneous, recovery and reuse
of the catalyst is not possible.

c) The catalyst needs to be separated for the product to be useful which is a
difficult process.
d) High concentrations of pyridine are not desirable due to its hazardous
nature.
e) The catalyst are either soluble or made from non-porous heterogeneous
polymer.
The main object of the present invention is to provide an improved process for the
preparation of copper bound to macroporous bis (picolyl) amine polymers that
overcomes the above stated drawbacks.
Another object of the present invention is to provide an efficient catalyst for the
preparation of poly (phenylene oxide) which greatly reduces the use of hazardous
chemicals such as pyridine in the conventional reaction.
Yet another object of the present invention is to prodvide an efficient catalyst for the
preparation of poly (phenylene oxide), wherein the catalyst can be easily recovered and
reused.
Yet another object of the present invention is to prodvide a catalyst for the preparation
of poly (phenylene oxide) wherein metal contamination of the product is eliminated.
Accordingly, the present invention provides a process for the preparation of copper
bound bis (picolyl) amine polymer which comprises reacting macroporous bis (picolyl)
amine polymers in the presence of copper salts in an aqueous medium at a pH of 2 to 6
or organic solvent such as herein described at a temperature in the range of 25 to
35°C, for a period ranging from 12 to 24 hours, removing the macroporous copper ion
containing bis (picolyl) amine polymer by conventional methods, followed by washing
and drying by known method to obtain copper bound bis (picolyl) amine polymer.

In an embodiment of the present invention, the macroporous bis(picolyl) amine polymer is prepared as described and claimed in our co-pending application number 790/D/97.
According to another embodiment of the invention, the copper salt used is selected from cupric chloride, cuprous chloride, copper nitrate, copper sulphate.
According to yet another embodiment of the invention, the aprotic solvent used may be dimethyl formamide, dimethyl sulfoxide, methanol, ethanol, tetrahydrafuran.
According to still another embodiment of the invention, the pH of the acidic aqueous medium may range from 2 to 6.
The invention is described herein below with reference to the examples which are illustrative only and should not be construed to limit the scope of this invention.
Example 1
0.100 gram of macroporous bis (2-picolyl) amine polymer beads was stirred with 100 ml cupric chloride solution buffered at a pH of
6.00 at 25°C for 24 hours. The contents were filtered after 24
hours, followed by washing with methanol for three times and drying. The yield obtained was 0.104 gram.

Example 2
0.100 gram of tnacroporous bis (3-picolyl) ataine polymer beads was stirred with 100 ml copper sulphate solution buffered at a pH of 6.00 at 30°C for 18 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.105 gram.
Example 3
0.100 gram of macroporous bis (2-picolyl) amine polymer beads was stirred with 100 ml copper nitrate solution buffered at a pH of 5.00 at 35°C for 12 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.105 gram.
Example 4
0.100 gram of macroporous bis (3-picolyl) amine polymer beads was stirred with 100 ml cupric chloride solution buffered at a pH of 4.00 at 25°C for 24 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.104 gram.
Example 5
0.100 gram of macroporous bis (3-picolyl) amine polymer beads was stirred with 100 ml cupric chloride solution buffered at a pH of 2.00 at 30°C for 24 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.103 gram.

Example 6
0.100 gram of macroporous bis (2-picolyl) amine polymer beads was stirred with 100 ml 0.01 % cupric chloride solution in dimethyl formamide at 25°C for 24 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.104 gram.
Example 7
0.100 gram of macroporous bis (3-picolyl) amine polymer beads was stirred with 100 ml 0.01 % cupric chloride solution in tetrahydrofuran at 35°C for 18 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.104 gram.
Example 8
0.100 gram of macroporous bis (2-picolyl) amine polymer beads was stirred with 100 ml 0.01 % cupric chloride solution in methanol at 25°C for 24 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.104 gram.
Example 9
0.100 gram of macroporous bis (2-picolyl) amine polymer beads was stirred with 100 ml 0.01 % cupric chloride solution in ethanol at 35°C for 12 hours. The contents were filtered after 24 hours, followed by washing with methanol for three times and drying. The yield obtained was 0.104 gram.

The process as described and claimed in the present invention offers the following advantages :
1. The catalyst is based on macroporous polymer matrix which is
neither hydrophobic nor hydrophilic. There is thus no
specific binding.
2. The catalyst being macroporous offers large surface area,
pore volume thus increasing the efficiency of the catalyst.
3. Copper is bound very effectively as noted from the stability
constants of homologous low molecular mass systems.
4. Any excess of pyridine gets complexed with the polymer
matrix thus not remaining in the soluble stream and
eliminating pollution related problems.

5. The polymeric catalyst can be easily separated and reused at
the end of the reaction.
6. Since the polymeric catalyst is heterogeneous and copper ion
is incorporated onto the polymer matrix, metal contamination
in the final product is totally avoided. '






We claim :
1. A process for the preparation of copper bound bis (picolyl) amine polymer which comprises reacting macroporous bis (picolyl) amine polymers in the presence of copper salts in an aqueous medium at a pH of 2 to 6 or organic solvent such as herein described at a temperature in the range of 25 to 35°C, for a period ranging from 12 to 24 hours, removing the macroporous copper ion containing bis (picolyl) amine polymer by conventional methods, followed by washing and drying by known method to obtain copper bound bis (picolyl) amine polymer.
2. A process as claimed in claim 1, wherein the copper salt used is cupric
chloride, cuprous chloride, copper nitrate, copper sulphate.
3. A process as claimed in claims 1-2 wherein the organic solvent used is
dimethyl formamide, dimethyl sulfoxide, methanol, ethanol,
tetrahydrafuran.
4. A process for the preparation of copper bound bis (picolyl) amine polymer
substantially as herein described with reference to the examples.

Documents:

1582-del-1999-abstract.pdf

1582-del-1999-claims.pdf

1582-del-1999-correspondence-others.pdf

1582-del-1999-correspondence-po.pdf

1582-del-1999-description complete.pdf

1582-del-1999-drawings.pdf

1582-del-1999-form-1.pdf

1582-del-1999-form-19.pdf

1582-del-1999-form-2.pdf


Patent Number 220150
Indian Patent Application Number 1582/DEL/1999
PG Journal Number 30/2008
Publication Date 25-Jul-2008
Grant Date 15-May-2008
Date of Filing 28-Dec-1999
Name of Patentee COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH
Applicant Address
Inventors:
# Inventor's Name Inventor's Address
1 SUNNY SKARIA
2 VARSHA BHIKOBA GHADGE
3 CHELANATTU KHIZHAKKE MADATH RAMAN RAJAN
4 SURENDRA PONRATHNAM
PCT International Classification Number B01J 23/72
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA